Abstract
AbstractThe quaternary sulfides K2AgVS4 and Rb2AgVS4 crystallize as dark violet needle‐like crystals with a metallic lustre. Infinite Ag‐ and V‐centered tetrahedra sharing common edges are running parallel to the crystallographic a axis. The chains are separated by K+ or Rb+ ions which are in an eightfold environment. The tetrahedra are occupied in an ordered fashion. The Ag–V interatomic distances amount to 2.904(1) and 2.910(1) A, respectively, which is significantly larger than the sum of the ionic radii of Ag+ and V5+. Whereas the V–S distances are in the normal range, the average (Ag–S) distances are the shortest reported so far indicating strong covalent bonding between monovalent Ag+ and S2–. In addition, the title compounds represent very rare examples of AgS4 polyhedra with equidistant Ag–S bonds. The geometrical parameters within the tetrahedra chains are only slightly affected when K+ is replaced by the larger Rb+ demonstrating the rigidity of the bonding properties within the tetrahedra. The compounds are isotypic with the quaternary copper sulfide K2CuVS4 and the selenides K2CuMSe4 (M=Nb, Ta).
Published Version
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